Unit 3.2 : Redox Reactions Flashcards
How are redox titrations carried out?
In the same way as acid-base titrations
What’s difference between acid-base titrations and redox titrations?
Redox titrations involve redox reactions
2 most important redox reagents in titrations
Potassium manganate (VII)
Sodium thiosulfate
Which important redox reagent isn’t used much in titrations anymore and why?
Potassium dichromate (VI), it’s carsinogenical
Half equation for the reduction of manganate (VII) ions in acidic solution
MnO4- + 8H+ + 5e- —> Mn2+ + 4H2O
What can manganate VII be described as?
An oxidising agent
What is potassium manganate (VII) used for in redox titrations?
To estimate the concentration of iron (II) ions in aqueous solution
Half equation for the oxidation of iron (II) ions
Fe2+ —> Fe3+ + e-
How do we form a full redox equation from half equations?
Balance the electrons
Full redox equation of potassium manganate (VII) and iron (II) ions
MnO4- + 5Fe2+ + 8H+ ——> Mn2+ + 5Fe3+ + 4H2O
Ratio of the number of moles of MnO4 to the number of moles of Fe2+
1:5
How is the titration between potassium manganate (VII) and iron (II) ions set up?
Potassium manganate (VII) in the burette, iron (II) complex in flask below
What’s the end point of the redox titration between potassium manganate (VII) and iron (II) ions?
Persisting pale pink
Briefly explain how the redox titration between potassium manganate (VII) and iron (II) ions would be completed
The potassium manganate (VII) solution is added from a burette to the iron (II) solution in the flask and the reaction is complete when the 1st permanent pink tinge is seen
What is the indicator in the redox reaction between potassium manganate (VII) and iron (II) ions?
There isn’t one - it’s self indicating
Why does potassium manganate (VII) not need an indicator?
Self-indicating
What colour does potassium manganate (VII) change to and from when the redox titration is complete?
Colourless to purple
What needs to be done to potassium manganate (VII) for a redox reaction to proceed satisfactorily?
Must be acidified
What do iron (II) do in air?
Readily oxidise
What needs to be done as iron (II) ions readily oxidise in air?
The solutions need to be acidified with dilute sulfuric acid to prevent oxidation
How does acid force the redox reaction to complete when added to the solution?
Removed the oxygen from the oxidising agent
What is the oxidising agent in the redox titration between potassium manganate and iron (II) ions?
Manganate (VII) ions
How much sulfuric acid are iron (II) ions acidified with to prevent oxidation?
1moldm-3
Why is sulfuric acid chosen as the acid to acidify potassium manganate (VII)?
It will not react with the manganate (VII) ions
Is potassium manganate (VII) an oxidising or a reducing agent?
An extremely powerful oxidising agent
How powerful of an oxidising agent is potassium manganate (VII)?
The most powerful oxidising agent which is reasonably stable in aqueous solution
What does potassium manganate do slowly in aqueous solution?
Decompose
What needs to happen to potassium manganate before it can be used in a redox titration reaction?
Needs to be standardised
What is usually used to standardise potassium manganate (VII) solution
Ammonium iron (II) sulfate
Why is ammonium iron (II) sulfate normally used to standardise potassium manganate (VII)?
It does not oxidise readily in solution and can be obtained to a high degree of purity
Why can’t iron (II) salts be used to standardise potassium manganate?
They cannot normal be obtained to a high degree of purity
Why would a brown precipitate of manganese (IV) oxide be formed during titration?
A neutral/alkaline solution must have been used
What would using a neutral/alkaline solution during the titration of potassium manganate (VII) result in
A brown precipitate of manganese (IV) oxide as a different reaction as taken place
What is the concentration of potassium manganate (VII) normally used during its redox titration?
0.02moldm-3
What does the concentration of the iron (II) ions need to be in it’s redox titration and how is this worked out?
About 0.100moldm-3 as the concentration of potassium manganate (VII) normally used is 0.02moldm-3 and they’re in a 1:5 ratio
What would adding iron (II) ions of concentration 0.100moldm-3 to potassium manganate (VII) of concentration 0.02moldm-3 do?
Complete reaction after the addition of 25cm3 of manganate (VII) solution to 25cm3 of the iron (II) solution
What tend to be self indicating in titrations?
Transition metals
How do we know exactly how much of a salt has been added in a reaction?
Mass of solid
Mass of solid + container
Mass of container
What happens to the solution that’s left unreacted at the end of a reaction?
It’s still present
Dichromate ions
Cr2O7^2-
Oxyanions
Negative ions that contain oxygen atoms bonded to another element
Negative ions that contain oxygen atoms bonded to another element
Oxyanions
Cr2O7^2- ion
Dichromate
Under which conditions can half equations for Oxyanions occur?
Either acidic or alkaline
Steps to constructing half equations for Oxyanions under acidic conditions
1.) balance the non-oxygen atoms
2.) balance the oxygen atoms by adding water molecules to the opposite side of the equation from the Oxyanion
3.) balance the hydrogen atoms from the water molecules by adding hydrogen atoms to the opposite side of the equation from the water molecules (i.e 0 the same side as the oxyanion)
4.) balance the overall charges on both sides of the equation by adding electrons to the side with the most positive overall charge (usually the same side a the hydrogen ions)
Steps to constructing half equations for Oxyanions under alkaline conditions
1.) balance the non-oxygen atoms
2.) for every oxygen atom in the oxyanion add a water molecule to the same side of the equation as the oxyanion
3.) balance the oxygen atoms by adding hydroxide ions to the opposite side of the equation from the water molecules and the oxyanion
4.) balance the overall charges on both sides of the equation by adding electrons to the side with the most positive overall charge (usually the opposite side from the hydroxide ions)
Which side of an equation usually has the most positive overall charge?
The side with the hydrogen ions, or the opposite side from the hydroxide ions
Ion/electron half equation for the reduction of acidified Cr2O7^2- to Cr3+
Cr2O7^2- + 14H+ + 6e- —> 2Cr3+ + 7H2O
Ion/electron half equation for the reduction of acidified MnO4- to Mn2+
MnO4 + 8H+ + 5e- —> Mn2+ + 4H2O
Ion/electron half equation for the oxidation of S2O3^2- to S4O6^2-
2S2O3^2- —> S4O6^2- + 2e-
2 extra ways to confirm if an oxyanion half equation is correct
If you have an oxidising agent, you need hydrogen ions
For every oxygen atom, we need twice the hydrogen atoms (as oxygen is -2)
What do you need if you have an oxidising agent?
Hydrogen ions
How do we combine half equations?
Balance he electrons by multiplying them out
Confirm that charges balance at the end
What do we do if we have hydrogen atoms on both sides of combined half equations?
We can simplify by subtracting the smaller amount from the other side
When can we simplify the combination of half equations and how?
When we have hydrogen atoms on both sides of the equation - by subtracting the smaller amount from the other side
Manganate (VII) ions
MnO4-
Are big numbers included in overall charge calculations?
Yes
What can the same simplifying method as used with hydrogen atoms when combining half equations be used for?
Waters
Thiosulfate ions
S2O3^2-
S2O3^2-
Thiosulfate ions
What is done as it isn’t straightforward to analyse a solution for copper (II) ions directly?
An indirect route is used
How is iodine formed during the titration involving copper (II) ions?
Addition of a colourless solution containing iodide ions, such as potassium iodide, to a blue solution containing copper (II) ions leads to the formation of a cloudy brown solution due to the formation of iodine
What type of solution contains iodide ions for the copper (II) titration?
A colourless solution, such as potassium iodide
What type of solution contains the copper (II) ions for their titration?
Blue
What colour does the solution turn upon adding a colourless solution containing iodide ions to a blue solution containing copper (II) ions to each other and why?
Brown due to the formation of iodine
Why is iodine formatted during the copper (II) ions titration?
Cu2+ ions in solution react with iodide ions to generate a brown solution of iodine
As well as reacting with iodide ions to generate iodine, what else happens to Cu2+ ions during their titration?
Reduced to copper (I) in a precipitate of CuI
Colour of precipitate formed by CuI
White
Colour of solution formed by iodine
Brown
Equation for the reaction between Cu2+ ions and iodide ions
2Cu^2+ + 4I- —> 2CuI + I2
What type of compounds are all reducing agents?
Halide ions
What are all halide ions?
Reducing agents
Strongest reducing agent from the halide ions
Iodide ions
What do we titrate the iodine formed during the reaction between Cu2+ and I- ions with?
With sodium thiosulfate of known concentration
Equation for sodium thiosulfate reacting with aqueous iodine in a redox titration
I2 + 2S2O3^2- —> 2I- + S4O6^2-
Molar ratio between iodine and thiosulfate
1:2
Iodine:thiosulfate
Half equation of iodine being reduced
I2 + e- —> 2I-
Half equation for the oxidation of thiosulfate ions
2S2O3^2- —> S4O6^2- + 2e-
Method for the redox titration for copper (II) ions
1.) add excess iodide ions (e.g - KI) to Cu2+(aq) to ensure that all of the Cu2+ reacts to produce I2. The mixture formed is a cloudy brown solution
2.) titrate the brown I2 (aq) against sodium thiosulfate (Na2S2O3) until the mixture is straw coloured
3.) add starch indicator which goes blue-black, and continue until the colour vanishes. The mixture is often described as flesh coloured
Why are excess iodide ions added during the titration for copper (II) ions?
To ensure that all of the Cu2+ reacts to produce I2
How long do we titrate brown I2 against sodium thiosulfate for?
Until the mixture is straw coloured
What colour does starch indicator go?
Blue-black
What goes in the flask during the titration for copper (II) ions?
Iodine solution
What comes from the burette during the titration for copper (II) ions?
Sodium thiosulfate solution
What is the indicator during the redox titration for copper (II) ions?
Starch solution
At which point is starch solution added during the redox titration of copper (II) ions?
Close to the end point
What is the end point of the redox titration for copper (II) ions?
When the blue colouration of the starch in the sodium thiosulfate and iodine solution just disappears
What has happened when the blue colour of the starch has gone during the redox titration for copper (II) ions?
All of the iodine has been used up
What type of sodium thiosulfate is used during the redox titration for copper (II) ions?
Standard sodium thiosulfate (may be standardised before use)
What is the use of iodine/sodium thiosulfate titrations?
To estimate the concentration of copper (II) ions in aqueous solution
Explain what is actually happening on a chemical level during the redox titration for copper (II) ions
Copper (II) ions undergo a redox reaction with iodide ions in aqueous solution
The iodide ions are oxidised to iodine, which can be titrated against sodium thiosulfate
The copper (II) ions are reduced to copper (I) ion, which precipitate as copper (I) iodide
Under which conditions do copper (II) ions undergo a redox reaction with iodide ions?
In aqueous solution
How do iodide ions turn into iodine that can be titrated against sodium thiosulfate for the redox titration for copper (II) ions?
They’re oxidised
What happens to the copper (II) ions during their redox titration?
Reduced to copper (I) ions, which precipitate a copper (I) iodide
How do copper (I) ions precipitate in the copper (II) ions redox titration?
As copper (I) iodide
How does copper (I) iodide appear?
An off-white precipitate
Why are excess iodide ions added during the redox titration for copper (II) ions (besides ensuring that all of the Cu2+ reacts)?
The iodine solution is complexed with unreacted iodide ions as a triiodide ion, I3-
Colour of iodine solution
Brown
What is the brown iodine solution complexed with?
Unreacted iodide ions as a triiodide ion, I3-
How does iodine appear at room temperature?
A grey solid that sublimes to a purple vapour
How could we make the redox titration for copper (II) ions faster?
By adding the excess iodide ions in solid form
Molar ratio between copper (II) ions and iodine molecules
2:1
Molar ratio between a molecule of iodine and thiosulfate ions
1:2
Molar ratio between thiosulfate and copper
1:1
How do we know that the molar ratio between thiosulfate and copper is 1:1?
Copper (II) ions to iodine —> 2:1
Iodine to thiosulfate ions —> 1:2
Combined…
2Cu2+ = 1I2 = 2S2O3^2-
Ethanedioate ions
C2O4^2-
C2O4^2- ions
Ethanedioate
How do we work out what’s oxidised and what’s reduced for Ecell calculations?
Write the full equation (combining the half equation) and work it out from this
Hi
Ok
Why do we have to standardise potassium manganate (VII)?
Since it:
- may absorb moisture from the environment
- may not be in its purest form